Hydrogen fluoride recovery process



May 3, 1949. J. o. lvERsoN HYDROGEN FLUORIDE RECOVERY PROCESS Filed March 24, 1,944

A NW &

Mr/zeg.

UNITED STATES PATENT OFFICE 2,468,756 HYDROGEN FLUORIDE RECOVERY PROCESS John O. Iverson, Chicago, Ill., assigner to Unl- .versal Oil Products Company, Chicago, lll., a

corporation of Delaware Application March 24, 1944, Serial No. 527,918

Claims. (Cl. 26o-683.4)

1 v This application is a continuation-impart of my co-pending application Serial #404,607, led

July 30, 1941, now Patent No. 2,388,918, issued November 13, 1945.

2 maining hydrocarbon reaction products to fractionation for the separation of an unconverted isobutane fraction and a motor fuel product, returning said isobutane fraction to the alkylating This invention relates to an improved process o Zone. withdrawing from the previously mentioned for the reaction of isoparairins with olefins in settling zone e portion of the used hydrogen fluorthe presence of a hydrogen uoride catalyst and ide catalyst, fractionting Said porting of used is more particularly concerned with a method of catalyst to seperate purified hydrogen uorde regenerating the used catalyst, from heavy organic materials and a mixture of The reactionl of isoparafiins with oienns in the 1o water end hydrogen fluoride and condensing and presence of a hydrogen iiuoride catalyst is an returning the Purified and dried hydrogen uoimportant method of producing saturated ride to the alkylating Zonebranched chain hydrocarbons having high anti- Hydrogen fluoride is slightly soluble in hydroknock values and suitable for usel in aviation Carbons- Therefore, the Products from the reacfuels. In the usual manner 0f conducting this 15 tion Zone will contain a small amount of the Order process, a liquid mixture of isoparaflins and oleof 1% of dissolved hydrogen fluoride- The fracns is agitated together with a liquid hydrogen tionation step following the reaction zone may be uoride-containing `catalyst until the reaction is Operated S0 aS to remove propane, butene, Or other complete and the resultant mixture is then allight hydrocarbons and also the dissolved hydrolowed to settle in order to separate the hydro- 20 gen fluoride. Upon condensation of the overhead carbon reaction products from the catalyst. stream. the hydrogen uoride forms a separate Heretofore various complicated schemes have layer Which may be returned to the alkyletion been proposed for the regeneration of the spent Zone and the Condensed hydrocarbons are reoataIyst. In this invention, a simpiined acid returned to the fractionation step. In order to regeneration step is shown which materially remove the hydrogen fluoride which has a higher duces the catalyst requirements in the operation boiling point than either bi1-tane o1 Propane, and the actual overall oost of the operation. it is necessary to vanorize a relatively large quan- Broadly the present invention comprises a titir of hydrocarbons If no Propone is t0 be reprocess for alkylating isoparaffins with olefns moved from the reaction products, the hydrogen which includes the steps of contacting said isofluoride may be removed by Vaporizing, condensparafns and olens with a hydrogen uoride ing and reuXing higher boiling hydrocarbonscatalyst under alkylating conditions, separating This step of removing and recovering the disthe hydrocarbon reaction products from the used solved hydrogen fluoride from the product is catalyst, returning at least a portion of said used important because the Presence of hydrogen nuocatalyst to the alkylating zone, recovering puried ride in the nished product would present a serihydrogen uoride from another portion of said ous corrosion problem, decrease the usefulness of used catalyst, separately recovering dissolved hythe nal product and increase the amount of drogen fluoride from the hydrocarbon reaction catalyst that would have to be added as make-up products and returning the hydrogen iluoride reto the process. covered in each of said last two steps to the al- Any suitable apparatus or reactor may be emkylation zone. ployed to contact the hydrocarbon reactants with In one specific embodiment, the invention comthe liquid catalyst in the reaction zone. It is prises a process for reacting isobutane with norimportant that very intimate contact be mainmally gaseous olens in the presence of a hydrotained between the two liquids for a period of gen fluoride catalyst under alkylating conditions, time sufflcient for the reaction. In general, Some introducing'the reaction mixture into a settling form of agitation such esmxing, stirring, etc.. zone wherein a substantial proportion of the used is used which forms an intimate mixture or hydrogen nuoride catalyst is separated from the emulsion of the hydrocarbons and hydrogen hydrocarbon reaction products, returning at least fluoride. In one particular form 0f apparatus, a portion of said used hydrogen iluoride catalyst as illustrated in the attached drawing, this agito the alkylation zone, subjecting the separated tation is obtained by the use of a motor driven hydrocarbon reaction products to fractionation stirrer and the reaction products and hydrogen for the removal of dissolved hydrogen uoride uoride continuously withdrawn to a settling overhead, condensing and returning the hydrogen zone and various fractionating zones wherein the fluoride to the reaction zone, subjecting the rehydrogen nuoride catalyst and unconverted hy- 3 drocarbons are separated and recycled to the reaction zone.

The hydrogen fluoride catalyst tendsto lose a substantial proportion of its activity after a period of use. -This decrease in activity is mainly due to two factors, namely, the contamination of the hydrogen fluoride with organic material and the dilution of the hydrogen fluoride with water. Although it is not known whether the nature of the contamination is a solution effect or a loose chemical combination, it has been discovered that this contaminating organic material can be removed and the activity of the catalyst restored by heating and distilllng off the active hydrogen fluoride. A heavy organic material remainsafter the distillation.

Hydrogen fluoride has a great affinity for water, and it is very difficult to remove the Water from the catalyst by any of the ordinary dehydrating methods. Although the incoming charge may be very nearly dry, nevertheless the catalyst will gradually accumulate water. This water will not only reduce the catalyst activity but also makes the hydrogen fluoride more corrosive to the apparatus in which it is handled. It is desirable to maintain the" concentration of water in the hydrogen fluoride below about It is an object of the present invention to provide a simplified method of separating a substantially dry hydrogen fluoride from the heavier high boiling organic materials and a hydrogen fluoride water mixture. This separation is accomplished in a single fractionation step wherein a stream of spent hydrogen fluoride catalyst is introduced and contacted with a stripping medium comprising heated isobutane, the purified hydrogen fluoride and isobutane being removed overhead while organic material and a mixture of water and hydrogen fluoride containing about 35 to 40% of hydrogen fluoride or some other mixture of higher hydrogen fluoride content removed as bottoms.

.An important feature of this fractionation step is the use of the heated isobutane stream as a supply of heat for the fractionation and as a stripping medium. If the ordinary methods of heating are employed such as reboilers with steam or other heating fluids, the heavier organic materials tend to form heavy carbonaceous deposits on the other surface of the reboiler thereby decreasing the efficiency of the heat transfer and at some point in the operation, this deposition will be so great that efficient heat transfer can not be accomplished and the operation must be discontinued to remove the carbonaceous deposit. The introduction of a heated stream of isobutane or other light hydrocarbons not only provides the best method for introducing heat into the fractionation zone by direct contact with the spent catalyst, but also supplies additional vapors to strip the hydrogen fluoride from the organic material and mixture of Water and hydrogen y fluoride.

The accompanying diagrammatic drawing illustrates one specii'lc form of apparatus embodying the features of the invention in which the process may be conducted.

Referring to the drawing, a normally gaseous charge consisting essentially of isobutane, butylenes and butane isvcombined with Aa recycled isobutane fraction from line 54 in line I and the mixture introduced through valve 2 into` charge pump 3 which discharges through line 4 containing valve 5 into alkylation zone v6 which is provided with an agitator 1 driven by motor 8 and the interaction of the oleflnic and isoparafnic hydrocarbons effected in 'zone 6, in the presence of hydrogen fluoride introduced through line I1. Generally some means of removing the heat of reaction from zone 6 must be provided, e. g., an internal cooler or a heat exchanger not shown. The emulsion of hydrocarbons and hydrogen fluoride from zone 6 is withdrawn through line 9 and valve Il! to settler I I wherein hydrogen fluoride settles out as the lower layer. A substantial portion of this catalyst layer is withdrawn through line I4 containing valve I5 by pump I6 which discharges through line I1 containing valve I8 into alkylation zone 6. Fresh hydrogen fluoride is introduced into the system through line I2 containing valve I3. The hydrocarbon layer from settler II passes through line I9 containing valve 20 and is introduced into fractionator 2l. In this column, the hydrogen fluoride which was dis-- solved in the hydrocarbon reaction products is separated as an overhead product through line 22 containing valve 23 through condenser 24 and the condensed material directed through line 25 containing valve 26 into receiver 21. In order to remove substantially all of the dissolved hydrogen fluoride from the hydrocarbon products, it is necessary to supply a relatively large quantity of hydrocarbon reflux to column 2|. The hydrogen fluoride removed overhead is present in receiver 21 in substantial excess of the solubility in the hydrocarbon present, and, therefore, two layers are formed. The lower hydrogen fluoride layer is withdrawn through catalyst return line 35 containing valve 36, pump 31 which discharges through line 38 and valve 39 into line I4 through which it is recycled to alkylation zone 6. A substantial portion of the upper hydrocarbon layer in receiver 21 is withdrawn through line 30 and valve 3I into pump 32 which discharges through line 33 containing valve 34 and returned as a reflux to column 2|. Any gaseous propane which may be present in receiver 21 is removed through line 28 containing valve 29. The bottoms product from fractionator 2| is withdrawn through line 40 containing valve 4 I and directed into fractionator 42. From this fractionator, the overhead product consisting mainly of isobutane is withdrawn through line 45 into condenser 46 and the condensed material passed through valvev41 into receiver 48. The isobutane is withdrawn through line 5I and valve 52 into pump 53 which discharges through line 54 and valve-55 into line I as hereinbefore set forth. If any light gases are present in receiver 48, they are vented through line 49 and valve 50. A product comprising normal butane and alkylate is withdrawn from fractionator 42 through line 43 containing valve 44.

As previously set forth, the catalyst in the reaction zone gradually becomes contaminated with heavy organic materials and water. In order to maintain the catalyst activity at a substantially constant level, a portion of the catalyst is withdrawn from the system, regenerated and recycled as hereinafter set forth. A portion 'of' the hydrogen fluoride layer separated from-the hydrocarbons insettler II is withdrawn through line 11 and valve 18 into pump 19 and introduced into heater 89 and thenceinto fractionator 58 through either of lines or 82 containing valve 8| and 83 respectively. The point of ,introduction of the spent acid will be dependent upon the extent of stripping desired in fractionator 58. Heated isobutane is introduced into the bottom of column 58 through line 84 containing valve 85 or a portion of the recycled isobutane stream in line 45 may be withdrawn through line 56 containing The space time defined as'the volume of catavalve 51 passed through a heating zone not shown and introduced into the bottomof fractionator Il. The overhead product from column il consisting mainly of isobutane and puried hydrogen fluoride is withdrawn through line l! containing valve 60, passed through condenser 6|, line 62 and valve 63 and collected in receiver 0I in which again two layers settle out, the upper layer being the hydrocarbon and the lower layer purified hydrogen fluoride. The lower layer of puried hydrogen fluoride is recycled from receiver 04 through line 81 and valve I! to pump 89 which discharges through line 1l containing valve 1l into line Il through which it is recycled into alkylating zone 8.

Hydrocarbons separated in receiver M are withdrawn through line 12 and valve 11 into pump 14 which discharges through line 1l and through valve 16 into column 58 as a reflux medium. 'I'he fractionation in column 5l is controlled by the pressure and temperature therein and the amount of reflux used to provide a hydrogen fluoride product having an acidity in excess of about 90% by weight and ordinarily running about 94 to 96% with a water content ordinarily below about 2% by weight. amount of reflux employed in acid regeneration zone l will be dependent primarily upon the amount of water in the. spent acid, higher percentage of water necessitating higher reiiux rates. If the water content is small, satisfactory overhead products may be obtained with little or no reflux. The remaining portion of the overhead product will consist of hydrocarbons principally isobutane which can be recycled to the reaction zone together with the purified HF through pump I9. The bottoms product from fractionator 5l is withdrawn through line containing valve 81 and consists primarily of the 'constant boiling mixture of water and hydrogen fluoride and a tar which is composed of the heavy organic materials present in or formed from the original spent catalyst. I'he hydrogen fluoride concentration `in the constant boiling mixture will ordinarily be around to 40% hydrogen iluoride although it will vary depending upon the particular conditions of temperature and pressure in the column and the amountV of heated isobutane introduced as a stripping medium. 'I'he constant boiling mixture and tar may be passed through a settling zone wherein theA organic material is separated from the constant boiling mixture and the separated fraction may be treated in any manner to recover the desirable constituents.

Acid regeneration zone It will ordinarily be quite small since it will be working on only. a portion of the hydrogen fluoride being used in the process. It should preferably be constructed of materials that will withstand the corrosive effects of hydrogen fluoride-water mixtures which accumulate and are withdrawn from the column. Copper and silver-lined vessels have been found to be very satisfactory for this purpose.

.The preferred range of operating conditions which may. be employed in an apparatus such as illustrated and above described for conducting the processes of the invention may be approximately as follows: The pressure at the outlet of charge pump 3 and in the reaction zone may be from about 125 to about 200 pounds per square inch or higher, although it is only necessary to use enough pressure to maintain both catalyst and hydrocarbon substantially in liquid phase. The temperature in the reaction zone may be lyst in the reaction zone divided by the volumesl per minute of hydrocarbon feed to the reaction zone may be about 5 to about 80 minutes. Although the ratio of hydrocarbon to hydrogen uoride in the reaction zone may vary considerably, a suitable ratio will be in the range of 0.5 to 10 volumes of hydrocarbon to one volume of hydrogen fluoride. The ratio o isoparamn to olen in the combined feed to a reaction zone may also vary considerably depending upon other conditions but will ordinarily be in the range from about 1 to 10 molecular proportions of isoparaiiin for one molecular proportion of olen.

A specific example of an operation of-the process as it is conducted in an apparatus such as illustrated and described is as follows:

The charging stock is a residual BB fraction from refinery gases-containing 1.1% fpropane. 11% of isobutylene, 17.7% of normal butylene, 39.8% of isobutane and '30.4% of normal butane on a volume basis. This charging stock is under suiiicient pressure to be liquid as supplied to line I and is discharged from pump 3 at a pressure of aboutv 150 pounds per square inch, combined with an isobutane recycle fraction from line 54 and contacted with a hydrogen uoride catalyst in reactor 6 which is maintained at a tempera-- ture of about F. The ratio of isobutane to oleilns inthe reaction zone is about 6:1. The reacting materials are withdrawn from reactor i through line 9 into settler Il wherein two layers are formed, the hydrogen uoride catalyst layer being the bottom layer. The upper hydrocarbon layer is withdrawn and treated as explained in a description of the accompanying drawing.- The ASTM octane number of the ilnal product is about 93.

A portion of the spent acid is withdrawn from settler Il, heated to a temperature of about 300 F. and introduced into fractionator 58 wherein it is contacted with a heated stream of isobutane introduced into the lower portion of fractionator 58. The temperature of the isobutane stream is about 400 F. The overhead product from regeneration zone 58 has a total acidity of about 95.9% by weight, water content of 1.2% and the remainder, light hydrocarbons. This acid is recycled to reaction zone 6. The bottoms from regeneration zone 58 consists of tar and a constant boiling HF water mixture containing about 50% by weight of HF. This bottoms product may be treated to separate the HF water mixture from the hydrocarbons and utilized in any manner desirable. By this simple method oi acid regeneration, a considerable increase in length of catalyst life is obtained with an appreciable decrease in the amount of make-up acid necessary.

I claim as my invention:

1. A process for the regeneration of a contaminated hydrogen iiuoride catalyst containing water and relatively heavy organic material which comprises introducing said contaminated catalyst into the upper portion of a fractionating column, introducing preheated light hydrocarbon vapors into the lower portion of said fractionating column at a temperature sufficient to decompose organic iiuorine compounds contained in said organic material and to vaporize hydrogen fluoride therefrom, passing said light hydrocarbon vapors upwardly in countercurrent contact with said contaminated catalyst, simultaneously stripping hydrogen fluoride vapors from said within the range of about 0 F. to about 150 F. 15 water and said heavy organic material by the upwardly owing light hydrocarbon vapors, removing overhead `from said column said light hydrocarbon vapors and substantially anhydrous hydrogen iiuoride vapors, and withdrawing from the bottom of said column a liquid mixture of said heavy organic material, hydrogen fluoride, and water.

2. The process of claim 1 wherein said contaminated catalyst isv subjected to a heating step prior to its introduction into said fractionating column.

3. The process of claim 1 wherein said light hydrocarbon comprises isobutane.

4. The process of claim 1 further characterized in that the hydrogen iiuoride and water withdrawn from the bottom of said column are in substantially the constant boiling mixture proportions. v

5. A process for the regeneration of a contaminated hydrogen iluoride catalyst containing water and relatively heavy organic material which comprises introducing said contaminated catalyst into the upper portion of a fractionating column, introducing preheated light hydrocarbon vapors into the lower portion of said fractionating column at a temperature suilcient to decompose organic fluorine compounds contained in said organic material and to vaporize hydrogen fluoride therefrom, passing said light hydrocarbon vapors upwardly in countercurrent contact with said contaminated catalyst, simultaneously stripping hydrogen uoride vapors from said Water and said heavy organic material by the upwardly flowing light hydrocarbon vapors, removing overhead from said column said light hydrocarbon vapors, condensing the overhead vapors to form a regenerated hydrogen fluoride layer and a hydrocarbon layer, withdrawing said regenerated hydrogen fluoride layer, returning at least a part of said hydrocarbon layer to theupper portion of said column as reiiux, and withdrawing from the bottom of said column a liquid mixture of said heavy organic material, hydrogen fluoride, and water.

6. The process of claim 5 wherein said isoparan is isobutane.

7. In the alkylation of isoparaflns with olefins in the presence of a hydrogen fluoride catalyst wherein an isoparafiin and an olefin are contacted with hydrogen uoride in an alkylation zone at alkylating conditions, the resultant reaction mixture is separated into a catalyst phase and a hydrocarbon phase comprising alkylate and unreacted isoparafiln, and a portion of said catalyst phase is recycled to said alkylation zone, and wherein said catalyst phase gradually accumulates undesirable amounts of heavy organic material and water, the improvement which comprises introducing atleast a part of the contaminated catalyst phase into the upper portion of a fractionating column, introducing preheated light hydrocarbon vapors into the lower portion of said fractionating column ata temperature sufficient to/ decompose organic uorine compounds contained in said organic material andcountercurrent contact with said contaminatedc'atalyst, simultaneously stripping hydrogen iluoride vapors from said water and said heavy organic material by the upwardly ilowing light hydrocarbon apors, removing overhead from said column said light hydrocarbon vapors and sub'- stantially anhydrous hydrogen fluoride vapors, condensing the overhead vapors to form a regenerated hydrogen iluoride layer and a hydrocarbon layer, returning said regenerated hydrogen iluoride to the alkylation zone, returning at least a part of said hydrocarbon layer to the upper portion of said column as reiiux. and withdrawing from the bottom of said column a liquid mixture of said heavy organic material, hydrogen iuoride, and water.

8. The process of claim 7 further characterized in that said light hydrocarbon comprises isobutane.

9. A process for the regeneration of a c'ontaminated hydrogen fluoride catalyst containing water and relatively heavy organic material which comprises introducing said contaminated catalyst into the upper portion of a fractionating column, introducing preheated light hydrocarbon vapors' into the lower portion of said fractionating column at a temperature 'suilcient to decompose organic' fluorine compounds contained in said organic material and to vaporize hydrogen iiuoride therefrom, passing said light hydrocarbon vapors upwardly in countercurrent contact with said contaminated catalyst, simultaneously stripping hydrogen uoride vapors from said water and said heavy organic material by the upwardly flowing light hydrocarbon vapors, removing overhead from said column said light hydrocarbon vapors and .substantially anhydrous hydrogen iluoride vapors, condensing the vapors removed overhead from said column and returning a portion of the resultant condensate to the upper portion of the column as reflux, and withdrawing from the bottom of said column a liquid mixture of said heavy organic material, hydrogen fluoride, and water.

10. The process of claim 9 further characterized in that said preheated light hydrocarbon vapors comprise isobutane.

JOI-IN O. IVERSON.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS l Matuszak Mar. 13, 1945 

